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Polymerization of fluoromonomers using a 3-allyloxy-2-hydroxy-1-propanesulfonic acid salt as surfactant

a technology of fluoromonomers and surfactants, applied in the field of polymerization of fluoromonomers, can solve the problems of affecting the molecular weight and other properties of products, the increasing scrutiny of perfluorinated surfactants, and the reduction of the reaction ra

Inactive Publication Date: 2005-03-22
ARKEMA INC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The term “polymer” is intended to be inclusive of homopolymers, copolymers, terpolymers and higher polymers.
The term “fluoropolymer” means a polymer formed by the polymerization of at least one fluoromonomer. Preferred fluoropolymers include, for example, polyvinylidene fluoride and copolymers containing at least 50 mole percent of vinylidene fluoride copolymerized with at least one comonomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinyl fluoride, pentafluoropropene. Other co-mono

Problems solved by technology

Non-fluorinated surfactants typically are not used, because they have the disadvantages of inhibiting the reaction, and affecting the molecular weight and other properties of the product, such as color.
The use of perfluorinated surfactants has recently become the focus of increasing scrutiny due to safety and environmental concerns.
However, this modification served to substantially lower the rate of the reaction.
The metal salts can, however, contaminate the product.

Method used

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  • Polymerization of fluoromonomers using a 3-allyloxy-2-hydroxy-1-propanesulfonic acid salt as surfactant
  • Polymerization of fluoromonomers using a 3-allyloxy-2-hydroxy-1-propanesulfonic acid salt as surfactant
  • Polymerization of fluoromonomers using a 3-allyloxy-2-hydroxy-1-propanesulfonic acid salt as surfactant

Examples

Experimental program
Comparison scheme
Effect test

example 1

Vinylidene fluoride polymerization (AHPS salt surfactant).

Into a 7.5 liter, a horizontally disposed stainless steel reactor was charged 4.100 kg of deionized water, 0.004 kg of paraffin wax, 0.400 kg of an aqueous solution of AHPS sodium salt (0.500 wt. %), and 0.0500 kg of an aqueous solution containing the radical initiator potassium persulfate (2.00 wt. %) and the buffering agent sodium acetate (2.00 wt. %). The reactor was purged with argon and agitated for 30 minutes at room temperature. The reactor was then sealed and heated to about 80° C. VF2 monomer (0.438 kg) was charged into the reactor to a pressure of about 4,480 kPa. The reactor temperature stabilized at about 82° C. Additional amounts of the initiator / buffer solution were added after 4 minutes (0.0300 L), and after 14 minutes (0.0200 L). Time intervals recorded for the reaction were measured from the time that the reactor was fully pressurized with the monomer. The reactor pressure was maintained at 4480 kPa by the ad...

example 2

Vinylidene fluoride polymerization (AHPS salt surfactant).

Into a 7.5 liter, horizontally disposed stainless steel reactor were charged 4.100 kg of deionized water, 0.004 kg of paraffin wax, 0.400 kg of an aqueous solution of AHPS sodium salt (0.258 wt. %), and 0.080 kg of an aqueous solution containing the radical initiator potassium persulfate (2.00 wt. %) and the buffer sodium acetate (2.00 wt. %). The reactor was purged with argon and agitated for 30 minutes at room temperature. The reactor was then sealed and heated to about 80° C. VF2 monomer (0.443 kg) was charged into the reactor to a pressure of about 4,480 kPa. The reactor temperature stabilized at about 82° C. The reactor pressure was maintained at 4480 kPa by the addition of VF2 als needed. The feed of monomer was stopped at 2.0 hours, after 2.380 kg VF2 had been fed to the reactor. Reaction temperature and agitation were maintained for another 0.3 hour. The reactor was then cooled to room temperature and vented. The reac...

example 3

Vinylidene fluoride polymerization (AHPS salt surfactant).

Into a 7.5 liter, horizontally disposed stainless steel reactor were charged 4.740 kg of deionized water, 0.004 kg of paraffin wax, and 0.200 kg of an aqueous solution of AHPS sodium salt (3.00 wt. %). The reactor was purged with argon and agitated for 30 minutes at room temperature. The reactor was then sealed and heated to about 80° C. VF2 monomer (0.408 kg) was charged into the reactor to a pressure of about 4,480 kPa. The reactor temperature stabilized at about 82° C. After the temperature stabilized, an aqueous solution (0.120 kg), containing the radical initiator potassium persulfate (3.50 wt. %) and the buffering agent sodium acetate (3.50 wt. %) was fed to the reactor. The reaction pressure was maintained at 4480 kPa by the addition of VF2 as needed. Additional amounts of initiator / buffer solution were added as follows during the reaction to maintain the reaction rate: 0.0100 L, after 0.804 kg of VF2 had been fed to t...

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Abstract

Fluoropolymers are prepared by a process comprising polymerizing at least one fluoromonomer in an aqueous reaction medium containing monomer, a radical initiator and a 3-allyloxy-2-hydroxy-1-propanesulfonic acid salt as surfactant. The medium may optionally contain one or more of an antifoulant, a buffering agent and a chain-transfer agent.

Description

FIELD OF THE INVENTIONThe present invention relates to methods of polymerization of fluoromonomers.BACKGROUND OF THE INVENTIONFluoropolymers are primarily produced via heterogeneous polymerization reactions, including suspension, emulsion and microemulsion systems. Generally, each of these reactions requires at least one monomer and a radical initiator in a suitable reaction medium. In addition, emulsion polymerizations of halogenated monomers generally require a surfactant capable of emulsifying both the reactants and the reaction products for the duration of the polymerization reaction. The surfactant of choice in the synthesis of fluoropolymers is generally a perfluoroalkyl surfactant. The most common perfluoroalkyl surfactant in the production of halogenated polymers is ammonium perfluorooctanoate (APFO). Non-fluorinated surfactants typically are not used, because they have the disadvantages of inhibiting the reaction, and affecting the molecular weight and other properties of t...

Claims

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Application Information

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IPC IPC(8): C08F114/00C08F114/18C07C69/52C07C69/00C08F14/00C08F16/00C08F2/12C08F16/24C08F14/18C08F2/16C08F14/22
CPCC08F14/18C08F14/22C08F2/16
Inventor WILLE, ROICE ANDRUSHEDHLI, LOTFIDURALI, MEHDIANTOUN, SAYED YOUSSEF
Owner ARKEMA INC
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